CN101115788A - Method for coating expandable styrene polymer granules - Google Patents

Method for coating expandable styrene polymer granules Download PDF

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Publication number
CN101115788A
CN101115788A CNA2006800040197A CN200680004019A CN101115788A CN 101115788 A CN101115788 A CN 101115788A CN A2006800040197 A CNA2006800040197 A CN A2006800040197A CN 200680004019 A CN200680004019 A CN 200680004019A CN 101115788 A CN101115788 A CN 101115788A
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China
Prior art keywords
coating
forming agent
styrene polymer
water
eps
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CNA2006800040197A
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CN101115788B (en
Inventor
M·阿尔门丁格尔
K·哈恩
J·鲁赫
G·埃尔曼
B·施密德
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/224—Surface treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Paints Or Removers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A method for the production of coated, expandable, styrene polymer (EPS) granules by extrusion of a styrene polymer melt containing an expanding agent through a nozzle plate with subsequent underwater granulation, wherein the EPS granules are coated by coating agents that are soluble, emulsifiable or suspendable in water in the water circuit of the underwater granulator.

Description

The method of coating expandable styrene polymer granules
The present invention relates to a kind of by making the styrene polymer melt extrusion that comprises whipping agent pass through template; granulation and produce expandable styrene polymer (EPS) the particulate method of coating under water subsequently, but the coating-forming agent that wherein said EPS particle maybe can suspend in water with solubilized emulsification applies in the circulation waterway of tablets press under water.
The expandable polystyrene particle that is used for circumference adiabatic hydrophobic treatment is for example known by WO 97/4334 and EP-A 913 423.Hydrophobizers is adsorbed on the silica gel and in next-door neighbour's aftertreatment and dry back is applied to the EPS particle with this form.
Purpose of the present invention is for finding a kind of method of even coating EPS particulate cheap and simple, and this method also can be carried out under not to base material generation absorption.
Therefore we have found the described method of beginning.
The suitable coating compounds agent is amphiphilic or hydrophobic organic compound.In hydrophobic organic compound, especially can mention C 10-C 30Paraffin, the reaction product of N-methylol amine and derivative of fatty acid, C 9-C 11The reaction product of the pure and mild ethylene oxide of oxo process, propylene oxide or oxybutylene or poly-(methyl) fluoroalkyl acrylate or its mixture.These coating-forming agents can preferably use with the aqueous emulsion form.
Preferred hydrophobizers is to have 10-30 carbon atom in the carbochain and preferably have 10-70 ℃, especially the paraffin of 25-60 ℃ of fusing point.This class paraffin for example is included among commercially available BASF product RAMASIT KGT, PERSISTOL E and PERSISTOL HP and the AVERSIN HY-N and the CEROL ZN available from Sandoz available from Henkel.
Another kind of suitable hydrophobizers is made up of the arborescens reaction product of N-methylol amine and derivative of fatty acid such as fatty acid amide, amine or alcohol, and this for example is described among US-A 2 927 090 or the GB-A 475170.Its fusing point is generally 50-90 ℃.This resinoid for example is included among commercially available BASF product P ERSISTOL HP and the ARCOPHOB EFM available from Hoechst.
At last, poly-(methyl) fluoroalkyl acrylate also is fit to as polyacrylic acid perfluoro capryl ester.Back one material is included among commercially available BASF product P ERSISTOL O and the OLEOPHOBOL C available from Pfersee.
Feasible amphiphilic coating-forming agent is static inhibitor such as emulsifying agent K30 (secondary alkane sulfonate) or Vinlub such as Zerol GMS or tristearin.
For producing expandable styrene polymer of the present invention, whipping agent is sneaked in the polymer melt.Present method comprises step a) production melt, b) mixes c) cooling, d) transmission and e) granulation.In these steps each all can be by the combination of known equipment or equipment in the plastic working and carried out.In order to mix, suitable is static state or dynamic mixer such as forcing machine.Can with polymer melt by directly take out in the polymerization reactor or can be in mixing forcing machine or independent melt extruder by the melt polymerization composition granule and direct production.The cooling of melt can be carried out in mixing equipment or independent water cooler.Feasible prilling process for example for comminution granulation under the pressurized water, with rotating knife and by spray atomization cooling liqs or atomizing particle refrigerative comminution granulation.The equipment that is fit to carry out this method is arranged and for example is:
A) polymerization reactor-static mixer/cooler-tablets press
B) polymerization reactor-forcing machine-tablets press
C) forcing machine-static mixer-tablets press
D) forcing machine-tablets press
The styrene polymer melt that comprises whipping agent is extruded under preferred 160-240 ℃ the temperature and is passed through template usually at 140-300 ℃.Needn't be cooled to the second-order transition temperature zone.
According to the present invention, gained expandable styrene polymer (EPS) but particulate applies the coating-forming agent maybe can suspend in water by solubilized emulsification carries out in tablets press.
A kind of method of especially preferred production expandable styrene polymer comprises the steps:
If a) polymerizing styrene monomer and suitable copolymerisable monomer,
B) make the degassing of gained styrene polymer melt,
C) by static state or dynamic mixer at least 150 ℃, if under preferred 180-260 ℃ the temperature whipping agent and suitable additive are sneaked in the styrene polymer melt,
D) make the styrene polymer melt that comprises whipping agent be cooled at least 120 ℃, preferred 150-200 ℃ temperature,
E) if suitable adding additive or filler,
F) discharge by template with hole, wherein said hole the diameter of template outlet side be no more than 1.5mm and
G) in the presence of solution, emulsion or the suspension of coating-forming agent, will comprise the directly granulation under water after template of melt of whipping agent.
The feasible particle that can produce compressing grains and partial foaming in a particular manner of variable counterpressure in UWP.Usually, granulation is clung at 1-25, carries out under the pressure of preferred 5-15 crust.Even when using nucleator, the partial foaming at the template place of UWP still keeps controlled.
The EPS particle is used 0.01-0.5 weight % usually, and preferred 0.1-0.3 weight % coating-forming agent applies, and wherein described in each case amount is all based on solids content.The amount of the coating-forming agent that applies for example can be set via the concentration in the circulation waterway.Based on the solids content in the water, the amount that is generally used for the coating-forming agent in the circulation waterway of underwater pelletizer is 0.05-20 weight %, preferred 0.1-10 weight %.Be to obtain the constant coating quality, the concentration of circulation waterway floating coat agent for example should be metered into the coating-forming agent corresponding with the amount that applies EPS and keeps constant by constant.
The temperature of the circulation waterway in the underwater pelletizer should be lower than the second-order transition temperature of styrene polymer, so that the EPS particle is only coated from the teeth outwards and not by thorough impregnation.Temperature is preferably 5-80 ℃, especially 10-60 ℃.
Expandable polystyrene particle advantageously of the present invention can be used for producing the moulded product that continues to be exposed to water, for example is used for roof thermal insulation or circumference adiabatic plate, is used for floating body or water sensitivity wrapping material such as fish box.
Umber among the embodiment and percentage ratio are based on weight.
Water-intake rate is measured according to DIN 53 433, and water-permeable is measured by the following method: with diameter is that the pipe of 100mm sticks on the cystose that thickness is 100mm and charges into the high water column of 100mm.
After 24 hours, check to be determined at the following outlet that whether can be observed water of cystose.The decline of horizontal plane is measured with mm.Before experiment, cystose is regulated 24 hours down at 60 ℃ in loft drier.Be stained with described pipe by silicon rubber then.
Embodiment:
Coating-forming agent:
Persistol HP=is available from the hydrophobizers of BASF, comprise the aqueous emulsion Ramasit KGT=of resin (70 ℃ of fusing points) that 22.8% paraffin (fusing point 52-54 ℃) and 9.6% is derived from N-methylol melamine and stearylamide available from the hydrophobizers of BASF, comprise the aqueous emulsion of 16.6% paraffin (fusing point 52-54 ℃)
Plurafac LF=ethylene oxide and oxybutylene and C 9-C 11The reaction product of oxo alcohol
Embodiment 1-3
To comprise the polystyrene (M that the viscosity number of wherein having sneaked into 6 weight % Skellysolve As is 75ml/g w=185000g/mol, polymolecularity M w/ M n=2.6) polystyrene melt is used for embodiment.The melt that will comprise whipping agent is cooled to 190 ℃ by originally 260 ℃.
The mixture that will comprise polystyrene melt, whipping agent and fire retardant is pressed through the template (diameter in each hole: 0.75mm) with 32 holes with 60kg/h.The compressing grains that has narrow size-grade distribution by granulating equipment production under the pressurized water.
It is the liquid coating agent of 0.5-10 weight % or the aqueous emulsion form of hydrophobizers that the water coolant of granulation underwater is the concentration that is shown in table 1.For obtaining the constant coating quality, must keep the constant concentration of water floating coat agent.This can by by the piston surge pump directly with coating-forming agent with corresponding to the loss materials flow the constant circulation waterway that is metered into of amount realize.By the restricted flow compensation water loss that directly enters water tank.
The pre-frothing in vapour stream of these particles is stored 24 hours to produce the bead (20g/l) of foaming, then in airtight mould by steam melt production foam.
Contrast experiment C1
Compare experiment with embodiment is similar, but granulation underwater carries out in circulation waterway not existing under the hydrophobizers.
Table 1
Embodiment Hydrophobizers [based on the weight % of original EPS product] Water-intake rate [volume %] Watertightness [mm]
C1 - 5.8 28
1 0.1 Persistol HP 0.9 5
2 0.25 Persistol HP 0.2 2
3 0.25 Ramasit KGT 0.2 0.5
4 0.2 Plurafac LF 120 0.9 9

Claims (8)

1. one kind by making the styrene polymer melt extrusion that comprises whipping agent pass through template; granulation and produce expandable styrene polymer (EPS) the particulate method of coating under water subsequently, but the coating-forming agent that wherein said EPS particle maybe can suspend in water with solubilized emulsification applies in the circulation waterway of tablets press under water.
2. according to the process of claim 1 wherein amphiphilic or hydrophobic organic compound are used as coating-forming agent.
3. according to the method for claim 2, wherein with C 10-C 30Paraffin, the aqueous emulsion of the reaction product of N-methylol amine and derivative of fatty acid or poly-(methyl) fluoroalkyl acrylate or its mixture is as coating-forming agent.
4. according to the method for claim 2, wherein with C 9-C 11The reaction product of the pure and mild ethylene oxide of oxo process, propylene oxide or oxybutylene is as coating-forming agent.
5. according to the method for claim 2, wherein static inhibitor is used as coating-forming agent.
6. according to the method for claim 2, wherein Vinlub is used as coating-forming agent.
7. according to each method among the claim 1-6, wherein based on the solids content in the water, the amount of the coating-forming agent in the circulation waterway of underwater pelletizer is 0.05-20 weight %.
8. according to each method among the claim 1-7, wherein the temperature of the circulation waterway of underwater pelletizer is 5-80 ℃.
CN2006800040197A 2005-02-04 2006-02-03 Method for coating expandable styrene polymer granules Expired - Fee Related CN101115788B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102005005495A DE102005005495A1 (en) 2005-02-04 2005-02-04 Process for coating expandable styrene polymer granules
DE102005005495.1 2005-02-04
PCT/EP2006/050649 WO2006082232A1 (en) 2005-02-04 2006-02-03 Method for coating expandable styrene polymer granules

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CN101115788A true CN101115788A (en) 2008-01-30
CN101115788B CN101115788B (en) 2010-07-28

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EP (1) EP1846485B1 (en)
KR (1) KR101196173B1 (en)
CN (1) CN101115788B (en)
AT (1) ATE398647T1 (en)
BR (1) BRPI0607101A2 (en)
DE (2) DE102005005495A1 (en)
MX (1) MX2007008745A (en)
MY (1) MY143600A (en)
PL (1) PL1846485T3 (en)
WO (1) WO2006082232A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105985528A (en) * 2015-03-17 2016-10-05 波尔玛有限公司 Composite expanded articles using different types of expanded particles and process for producing the same

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL2121832T3 (en) 2006-12-18 2011-12-30 Basf Se Expandable styrene polymers and foams with decreased water absorption
DE102007050681A1 (en) * 2007-10-22 2009-04-23 Coperion Werner & Pfleiderer Gmbh & Co. Kg Method and device for producing a polymer granulate
DE102011119939A1 (en) * 2011-12-01 2013-06-06 Technische Universität Hamburg-Harburg Method of making a composite, the composite and the use of the composite to make certain products
DE102015220203A1 (en) * 2015-10-16 2017-04-20 Alois Edler Method and device for producing a polystyrene granulate

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0305862A1 (en) * 1987-09-04 1989-03-08 General Electric Company One-step process for the production of expandable foam beads
DE4009897A1 (en) * 1990-03-28 1991-10-02 Basf Ag FINE-PIECE EXPANDABLE STYRENE POLYMERS
MY117649A (en) * 1996-07-04 2004-07-31 Shell Int Research Process for the preparation of polymer particles

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105985528A (en) * 2015-03-17 2016-10-05 波尔玛有限公司 Composite expanded articles using different types of expanded particles and process for producing the same

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CN101115788B (en) 2010-07-28
DE102005005495A1 (en) 2006-08-10
KR101196173B1 (en) 2012-11-01
BRPI0607101A2 (en) 2010-03-09
PL1846485T3 (en) 2008-11-28
EP1846485B1 (en) 2008-06-18
EP1846485A1 (en) 2007-10-24
KR20070108217A (en) 2007-11-08
MY143600A (en) 2011-06-15
ATE398647T1 (en) 2008-07-15
DE502006000957D1 (en) 2008-07-31
WO2006082232A1 (en) 2006-08-10
MX2007008745A (en) 2007-08-06

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